JP2016000829A - Carbohydrate binding agent and material manufactured by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binding agent.SOLUTION: Disclosed is a binding agent comprising a polymer binding agent containing a product material between a carbohydrate reactant and a nucleophilic reagent; said binding agent is useful for firmly solidifying loosely combined objects such as fibers; also disclosed is a fiber product material comprising fibers in contact to a carbohydrate reactant and a nucleophilic reagent; the binding agent composition can be hardened so as to produce a fiber product material comprising fibers bound by a crosslinked polymer; and further disclosed is a method for binding fibers with a binding agent based on a carbohydrate reactant and a polyamine.

Description

(Cross-reference to related applications)
This application claims the benefit of US Provisional Patent Application No. 61 / 332,452, filed May 7, 2010. This US Provisional Patent Application No. 61 / 332,452 is incorporated herein by reference.

  The present disclosure relates to binder formulations, materials made using the same and containing carbohydrate-based binders, and methods for preparing the same. In particular, binders containing the reaction products of carbohydrates and nucleophiles and the materials made with them are described.

(background)
Binders are useful for making articles because they can solidify uncombined or loosely assembled objects. For example, a binder makes it possible to integrate two or more surfaces. In particular, the binder may be used to produce a product that includes strongly consolidated fibers. Thermosetting binders can be characterized by transformation into insoluble and infusible materials through heat or catalysis. Examples of thermosetting binders include various phenol-aldehydes, urea-aldehydes, melamine-aldehydes, and other condensation polymerization materials such as furan and polyurethane resins. Binder compositions containing phenol-aldehyde, resorcinol-aldehyde, phenol / aldehyde / urea, phenol / melamine / aldehyde, etc. are used to bond fibers, fabrics, plastics, rubber, and many other materials .

  The mineral wool and fiberboard industry has historically used phenol formaldehyde binders to bond fibers. Phenol formaldehyde type binders provide suitable properties for the final product. However, environmental considerations have prompted the development of alternative binders. One such alternative binder is a carbohydrate-based binder obtained from the reaction of a carbohydrate with a polyprotic acid, for example, US Pat. Another alternative binder is an esterification product obtained by reacting a polycarboxylic acid and a polyol. Since these binders do not use formaldehyde as a reagent, they are collectively referred to as formaldehyde-free binders.

  One area of current development is to find alternatives to phenol-formaldehyde type binders across the full range of products in the architectural and automotive sectors (eg, glass fiber insulation, particleboard, office panels, and sound insulation). is there. In particular, formaldehyde-free binders that have already been developed may not have all of the desired properties for all products in this sector. For example, binders based on acrylic acid and poly (vinyl alcohol) show promising performance characteristics in the future. However, this binder is more expensive than phenol-formaldehyde binders and is inherently derived from petroleum-based resources and tends to exhibit a lower reaction rate compared to phenol-formaldehyde-based binder compositions. (Requires long curing time or high curing temperature). Carbohydrate-based binder compositions are made with relatively inexpensive precursors and are derived primarily from renewable resources. However, these binders may require reaction conditions for curing that are substantially different from the conditions under which conventional phenol formaldehyde binder systems cure. Therefore, simple replacement of phenol formaldehyde type binders with existing alternatives has not been easily realized.

US Patent Application Publication No. 2007/0027283 International Publication No. 2009/019235 US Patent Application Publication No. 2005/0202224

(Summary)
According to the present disclosure, carbohydrate based binders are described. Binder compositions have properties that are useful in a variety of applications, and in particular binders can be used to bond loosely combined objects such as fibers.

  In an exemplary embodiment, the present disclosure relates to a binder comprising a polymer product of a carbohydrate reactant and a nucleophile. In one embodiment, the carbohydrate reactant is a polysaccharide. In one embodiment, the carbohydrate reactant is a monosaccharide or a disaccharide. In another embodiment, the carbohydrate is a monosaccharide that is in its aldose or ketose form. In another embodiment, the carbohydrate reactant is selected from the group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof. In another embodiment, the polymer product is a thermosetting polymer product.

In an exemplary embodiment, the nucleophile is difunctional. In another embodiment, the nucleophile is R ₁ -Q-R _2, wherein, Q is an alkyl, cycloalkyl, heteroalkyl or cycloheteroalkyl, said alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl Each heteroalkyl is optionally substituted and has a nucleophilic moiety and a stabilizing moiety, and R ₁ is an amine, azide, cyanate, isocyanate, thiol, disulfide, thiocyanate, halogen, haloformyl, carboxyl, carboxylate R ₂ is selected from the group consisting of amine, amide, imine, imide, imide, nitro, nitrate, pyridine, phosphate, phosphono, hydroxyl, hydrogen, sulfono, sulfo, sulfinyl, and sulfhydryl (thiol). Group Are al selected. In one embodiment, the nucleophile comprises an amine functional group.

  In an exemplary embodiment, the molar ratio of carbohydrate reactant to nucleophile is in the range of about 1: 1 to about 30: 1. In another embodiment, the molar ratio of carbohydrate reactant to nucleophile is in the range of about 2: 1 to about 10: 1. In another embodiment, the aqueous extract of the polymer product has a pH in the range of about 5 to about 9. In another embodiment, the aqueous extract of the polymer product is essentially colorless. In yet another embodiment, the polymer product is phenol-free and / or formaldehyde-free. In another embodiment, the aqueous extract of the polymer product can reduce the Benedict reagent. In another embodiment, the polymer product absorbs light between 400 and 500 nm, for example, in one embodiment, absorbs 420 nm light.

  In an exemplary embodiment, a method of making an object assembly bonded with a polymer binder comprises preparing a solution containing a reactant and a solvent to produce a polymer binder, the reactant Including a carbohydrate reactant and a nucleophile; placing the solution on the object assembly; volatilizing the solvent to form an uncured product; and the carbohydrate reactant and nucleophile. Subjecting the uncured product to conditions that allow the nucleating agent to polymerize to form a polymeric binder. In one embodiment, the object assembly comprises mineral fibers (slag wool fibers, rock wool fibers, or glass fibers), aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, polyester fibers, rayon fibers, and cellulose fibers. A fiber selected from the group consisting of: In another embodiment, the object assembly includes particulates such as coal or sand. In another embodiment, the object assembly is glass fiber. In yet another embodiment, the glass fiber is present in the range of about 70% to about 99% by weight. In another embodiment, the object assembly includes cellulose fibers. For example, the cellulose fibers may be wood chips, sawdust, wood pulp, or crushed wood. In yet another embodiment, the cellulose fibers may be other natural fibers such as jute, flax, hemp, and straw.

  In an exemplary embodiment, the method of making a mass of objects bound with a polymer binder further comprises an amount of carbohydrate reactant and an amount of nucleophile, each in a molar ratio from about 2: 1. Preparing a solution by adding to a range of about 10: 1. In one embodiment, preparing the solution includes adding a carbohydrate reactant and a nucleophile to the aqueous solution. In another embodiment, the step of preparing the solution includes adjusting the pH of the solution within a range of about 8 to about 13, for example, in one embodiment within a range of about 8 to about 12.

In an exemplary embodiment, the present disclosure relates to a composition comprising an object assembly and a binder, the binder comprising a polymer product of a reaction between a carbohydrate reactant and a nucleophile, the polymer production The object is substantially water insoluble. In one embodiment, the object assembly comprises mineral fibers (slag wool fibers, rock wool fibers, or glass fibers), aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, polyester fibers, rayon fibers, and cellulose fibers. including. For example, cellulose fibers include wood chips, sawdust, wood pulp, and / or ground wood. In one embodiment, the carbohydrate reactant is selected from the group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof. In another embodiment, the nucleophile is selected from the group consisting of diamines, triamines, tetramines, and pentamines. In one embodiment, the nucleophile is R ₁ -QR ₂ , wherein Q is alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, and the alkyl, cycloalkyl, heteroalkyl, cyclohetero Each alkyl is optionally substituted, R ₁ is a nucleophilic moiety and R ₂ is a stabilizing moiety. In one embodiment, R ₁ is selected from the group consisting of amine, azide, cyanate, isocyanate, thiol, disulfide, thiocyanate, halogen, haloformyl, carboxyl, carboxylate, hydroxyl, and alkoxide. In another embodiment, R ₂ is selected from the group consisting of amine, amide, imine, imide, nitro, nitrate, pyridine, phosphate, phosphono, hydroxyl, hydrogen, sulfono, sulfo, sulfinyl, and sulfhydryl (thiol). .

In another embodiment, the composition further comprises a silicon-containing compound. In one embodiment, the silicon-containing compound is a functionalized silyl ether or a functionalized alkyl silyl ether, such as an amino functionalized alkyl silyl ether. For example, in one embodiment, the silicon-containing compound may be γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or aminoethylaminopropyltrimethoxysilane, or a mixture thereof. In another embodiment, the silicon-containing compound may be an amino functional oligomeric siloxane. In another embodiment, the composition is a corrosion selected from the group consisting of dust control oil, monoammonium phosphate, sodium metasilicate pentahydrate, melamine, tin (II) oxalate, and methyl hydrogen silicone fluid emulsion. Contains inhibitor.
In one embodiment, for example, the following items are provided.
(Item 1)
A binder comprising a polymer product of a carbohydrate reactant and a nucleophile,
(A) said nucleophile is _R 1 _{-Q-R 2,}
(B) Q is alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, each of said alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl is optionally substituted and has a nucleophilic moiety and a stabilizing moiety. And
(C) R ₁ is selected from the group consisting of amine, azide, cyanate, isocyanate, thiol, disulfide, thiocyanate, halogen, haloformyl, carboxyl, carboxylate, hydroxyl, and alkoxide;
(D) A binder wherein R ₂ is selected from the group consisting of amine, amide, imine, imide, nitro, nitrate, pyridine, phosphate, phosphono, hydroxyl, hydrogen, sulfono, sulfo, sulfinyl, and sulfhydryl.
(Item 2)
The binder of item 1, wherein the carbohydrate reactant is a polysaccharide.
(Item 3)
The binder of item 1, wherein the carbohydrate reactant is a monosaccharide or a disaccharide.
(Item 4)
The binding agent of item 1, wherein the carbohydrate reactant is a monosaccharide that is in its aldose or ketose form.
(Item 5)
The binder of item 1, wherein the carbohydrate reactant is selected from the group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof.
(Item 6)
6. A binder according to any one of items 1 to 5, wherein R ₁ and R ₂ form a covalent bond with the carbohydrate reactant to form the polymer product.
(Item 7)
The binder according to any one of items 1 to 6, wherein R ₁ is a nucleophilic moiety and R ₂ is a stabilizing moiety.
(Item 8)
The binder according to any one of items 1 to 7, wherein Q is an alkyl selected from the group consisting of C _{2 to} C ₂₄ .
(Item 9)
Q is an alkyl selected from the group consisting of C ₂ -C _8, binding agent according to any one of Items 1 to 7.
(Item 10)
The binder according to any one of items 1 to 7, wherein Q is an alkyl selected from the group consisting of C _{3 to} C ₇ .
(Item 11)
Q is C ₆ alkyl, binding agent according to any one of Items 1 to 7.
(Item 12)
The binder according to any one of items 1 to 7, wherein Q is selected from the group consisting of cyclohexyl, cyclopentyl, or cyclobutyl.
(Item 13)
8. A binder according to any one of items 1 to 7, wherein Q is benzyl.
(Item 14)
The binder according to any one of items 1 to 7, wherein R ₁ -QR ₂ is 2-[(2-aminoethyl) amino] ethanol.
(Item 15)
14. The binder according to any one of items 1 to 13, wherein R ₁ and R ₂ are each a thiol.
(Item 16)
14. A binder according to any one of items 1 to 13, wherein R ₁ is an amine.
(Item 17)
R ₂ are an amine, amide, imine or imide, binding agent according to item 16.
(Item 18)
R ₂ is an amine, binding agents of claim 16.
(Item 19)
19. A binder according to any one of items 1 to 18, wherein the molar ratio of the carbohydrate reactant to the nucleophile is in the range of about 1: 1 to about 30: 1.
(Item 20)
19. A binder according to any one of items 1 to 18, wherein the molar ratio of the carbohydrate reactant to the nucleophile is in the range of about 2: 1 to about 10: 1.
(Item 21)
21. The binder according to any one of items 1 to 20, wherein the aqueous extract of the polymer product has a pH in the range of about 5 to about 9.
(Item 22)
22. A binder according to any one of items 1 to 21, wherein the aqueous extract of the polymer product is essentially colorless.
(Item 23)
23. A binder according to any one of items 1 to 22, wherein the aqueous extract of the polymer product is capable of reducing a Benedict reagent.
(Item 24)
24. A binder according to any one of items 1 to 23, wherein the polymer product is phenol-free and formaldehyde-free.
(Item 25)
25. A binder according to any one of items 1 to 24, wherein the carbohydrate reactant and the nucleophile are non-volatile.
(Item 26)
26. A binder according to any one of items 1 to 25, wherein the solution in contact with the binder reduces the Benedict reagent.
(Item 27)
27. A binder according to any one of items 1 to 26, wherein the polymer product strongly absorbs 420 nm light.
(Item 28)
Preparing a solution containing a reactant and a solvent to produce a polymer binder, the reactant comprising a carbohydrate reactant and a nucleophile;
Placing the solution on an object assembly;
Evaporating the solvent to form an uncured product;
Subjecting the carbohydrate reactant and the nucleophile to subjecting the uncured product to conditions that cause formation of the polymeric binder, and producing a mass of objects bound by the polymeric binder. .
(Item 29)
29. A method according to item 28, wherein the object aggregate includes fibers selected from the group consisting of mineral fibers, aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, polyester fibers, rayon fibers, and cellulose fibers. .
(Item 30)
29. A method according to item 28, wherein the object assembly is glass fiber.
(Item 31)
32. The method of item 30, wherein the glass fiber is present in the range of about 70% to about 99% by weight.
(Item 32)
29. A method according to item 28, wherein the object assembly includes cellulose fibers.
(Item 33)
33. A method according to item 32, wherein the cellulose fiber is a substrate selected from the group consisting of wood chips, sawdust, wood pulp, and crushed wood.
(Item 34)
29. A method according to item 28, further comprising the step of packaging the uncured product in a packaging material suitable for storage.
(Item 35)
Preparing the solution includes adding an amount of the carbohydrate reactant and an amount of the nucleophile such that the weight ratio is in the range of about 2: 1 to about 10: 1. 29. The method according to item 28.
(Item 36)
29. The method of item 28, wherein preparing the solution comprises adding the carbohydrate reactant and the nucleophile to an aqueous solution.
(Item 37)
38. The method of item 36, wherein preparing the solution comprises adjusting the pH of the solution within a range of about 8 to about 12.
(Item 38)
A composition comprising an object assembly and a binder, wherein the binder comprises a polymer product of a reaction between a carbohydrate reactant and a nucleophile, wherein the polymer product is substantially water insoluble. Composition.
(Item 39)
40. The composition of item 38, wherein the object aggregate includes fibers selected from the group consisting of mineral fibers, aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, polyester fibers, rayon fibers, and cellulose fibers. object.
(Item 40)
40. The composition of item 38, wherein the object assembly comprises glass fibers.
(Item 41)
40. The composition of item 38, wherein the object assembly comprises cellulose fibers.
(Item 42)
42. The composition of item 41, wherein the cellulose fibers are present in a cellulose substrate selected from the group consisting of wood chips, sawdust, wood pulp, ground wood, jute, flax, hemp, and straw.
(Item 43)
43. A composition according to any one of items 38 to 42, wherein the carbohydrate reactant is selected from the group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof.
(Item 44)
44. A composition according to any one of items 38 to 43, wherein the nucleophile is a compound having a nucleophilic moiety and a stabilizing moiety.
(Item 45)
Said nucleophile is _R 1 _{-Q-R 2,} wherein
(A) Q is alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, each of said alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl is optionally substituted;
(B) R ₁ is the nucleophilic moiety,
(C) R ₂ is the stabilizing moiety,
45. A binder according to any one of items 38 to 44.
(Item 46)
46. A composition according to any one of items 38 to 45, further comprising a silicon-containing compound.
(Item 47)
The silicon-containing compound is selected from the group consisting of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, aminofunctional oligomeric siloxane, and mixtures thereof; 47. A composition according to item 46.
(Item 48)
47. A composition according to item 46, wherein the silicon-containing compound is γ-aminopropyltriethoxysilane.
(Item 49)
Items 38-48, further comprising a corrosion inhibitor selected from the group consisting of dust control oil, monoammonium phosphate, sodium metasilicate pentahydrate, melamine, tin (II) oxalate, and methylhydrogensilicone fluid emulsion. The composition as described in any one of these.

FIG. 1 shows a schematic diagram of the Maillard reaction resulting in the production of melanoidin. FIG. 2 shows a schematic diagram of a typical Amadori dislocation. FIG. 3 shows the curing temperature profile at the center of a glass fiber mat sample for different binders during a thermoforming cycle (X axis, molding time in minutes) using a molding press with a temperature controlled platen of 204 ° C. (Y axis, ° C.)). Binder 1 (♦) is a phenol formaldehyde binder (Comparative Example 2), Binder 2 (■) is a carbohydrate-inorganic acid binder (Comparative Example 3), and Binder 3 (x) is Dextrose-ammonia-hexamethylenediamine (HMDA) binder (Example 5).

(Detailed explanation)
While the invention is susceptible to various modifications and alternative forms, specific embodiments are described in detail herein. However, it should be understood that the invention is not intended to be limited to the particular forms described, but rather includes all modifications, equivalents, and alternatives that fall within the spirit and scope of the invention. is there.

  The present disclosure relates to binder compositions that have unexpected utility when solidifying uncombined or loosely combined objects. Binder compositions represent an unexpected advancement of the state of the art in the field of binder compositions. Specifically, the binder provides an improvement in performance and provides a simpler and advantageous manufacturing process, while maintaining the benefits consistent with the environment that is characteristic of carbohydrate-based binder systems. .

  The term binder solution as used herein is a solution of a chemical that can be substantially dehydrated so that an uncured binder is formed. The binder or binder composition used herein may be cured, may not be cured, or may be partially cured. The composition of uncured binder is referred to as the uncured binder composition. An uncured binder is a substantially dehydrated mixture of chemicals that can be cured to form a cured binder. Substantially dehydrated is the viscosity of the remaining material (including the binder reactant and solvent) as a result of vaporization of the solvent (typically water or a mixture thereof) used to make the binder solution. Means high enough to create a cohesive force between loosely assembled objects. Thus, the remaining material is an uncured binder. In one embodiment, the solvent is less than 65% of the total weight of the remaining material. In another embodiment, the substantially dehydrated binder has a water content between about 5% and about 65% by weight of the total binder. In another embodiment, the solvent may be less than 50% of the total weight of the remaining material. In yet another embodiment, the solvent may be less than 35% of the total weight of the remaining material. In another embodiment, the substantially dehydrated binder has between about 10% to about 35% water by weight of the total binder. In another embodiment, the solvent may comprise less than about 20% of the total weight of the remaining material.

  In exemplary embodiments, the uncured binder may be an at least partially water soluble, colorless, white, off-white, ocher, or yellow to brownish sticky material. As used herein, the term cured binder refers to a polymer product that cures an uncured binder composition. The cured binder may have a characteristic brown to black color. Although described as brown or black, another feature is that the binder tends to absorb light over a wide range of wavelengths. In particular, it may have a higher absorbance at about 420 nm. Because the polymer crosslinks extensively, the cured binder is substantially insoluble. For example, the binder is mostly insoluble in water. The uncured binder described herein provides sufficient binding capacity to firm the fibers. However, cured binders provide robust and long-lasting durability and physical properties commonly associated with crosslinked polymers.

  In an exemplary embodiment, the binder reactant described herein is soluble in water and the binder solution is a solution of the binder reactant in an aqueous solution. In one embodiment, the surfactant is included in the aqueous solution for the purpose of increasing the solubility or dispersibility of the one or more binder reactants or additives. For example, a surfactant may be added to the aqueous binder solution to increase the dispersibility of the particulate additive. In one embodiment, the surfactant is used to produce an emulsion with a nonpolar additive or binder reactant. In another embodiment, the binder solution comprises about 0.01% to about 5% by weight surfactant based on the weight of the binder solution.

  In an exemplary embodiment, the binder solution described herein adheres to the mineral fibers during the production of the mineral fiber insulation product (eg, sprays on the mat or fibers as it enters the forming area). To spray). When the binder solution contacts the mineral fibers, the residual heat of the mineral fibers (eg, the glass fibers are made from molten glass and therefore contain residual heat) and the air inside and / or around the product. The flow causes some of the water to evaporate from the binder solution. Removal of the water leaves the remaining components of the binder on the fiber surface as a coating of a sticky or semi-sticky high solids mixture. This coating of sticky or semi-sticky high solids mixture functions as a binder. At this point, the mat is not cured. In other words, the uncured binder functions to bind the mineral fibers to the mat.

  Furthermore, it should be understood that the uncured binder described above can be cured. For example, the process of manufacturing a cured insulation product may include a subsequent step of applying heat to cause a chemical reaction in the uncured binder composition. For example, when making a glass fiber insulation product, the uncured insulation product may be transferred to a curing furnace after the binder solution is attached to the fiber and dehydrated. In the curing oven, the uncured insulation product is heated (eg, from about 300 ° F. to about 600 ° F. [about 150 ° C. to about 320 ° C.]), thereby curing the binder. The cured binder is a formaldehyde-free water-resistant binder that binds the glass fibers of the insulation product together. Note that drying and heat curing may be performed sequentially, simultaneously, simultaneously, or simultaneously.

  In an exemplary embodiment, the uncured fiber product comprises from about 3% to about 40% dry binder solids (total uncured solids by weight). In one embodiment, the uncured fiber product comprises from about 5% to about 25% dry binder solids. In another embodiment, the uncured fiber product comprises about 50% to about 97% fiber by weight.

  As described herein with regard to mineral fiber surface binders, a cured binder is the product of curing a binder reactant. The term cured indicates that the binder has been exposed to conditions that initiate a chemical change. Examples of these chemical changes include, but are not limited to, (i) covalent bonds, (ii) hydrogen bonding of the binder component, and (iii) chemical cross-linking of polymers and / or oligomers in the binder. It is not a thing. These changes can increase the durability and solvent resistance of the binder compared to the uncured binder. Curing of the binder can result in the formation of a thermosetting material. Furthermore, the cured binder can increase the adhesion between objects in the assembly as compared to the uncured binder. Curing can be initiated, for example, by heat, microwave radiation, and / or conditions that initiate one or more of the above-described chemical changes. Without being limited to a particular theory, curing may include the reaction of a carbohydrate with a nucleophile in a nucleophilic addition reaction or a nucleophilic addition / elimination reaction.

  In situations where a chemical change in the binder results in the release of water, such as polymerization and cross-linking, curing is determined by the amount of water released beyond that which would have resulted from drying alone. Can do. Techniques used to measure the amount of water released during drying compared to curing the binder are well known in the art.

In an exemplary embodiment, the nucleophile is a nitrogen containing compound. In one embodiment, the cured binder composition includes a nitrogen-containing polymer. In one embodiment, the nitrogen-containing polymer is brown to black in color. Without being limited to a particular theory, the cured binder composition comprises a mixture of high molecular weight polymers. High molecular weight polymers can be characterized as being highly crosslinked. Furthermore, high molecular weight polymers can be characterized as brown, complex furan ring-containing and nitrogen-containing polymers. As used herein, high molecular weight includes polymers having a molecular weight in excess of 100,000 Daltons. By being composed of highly crosslinked polymer chains, the molecular weight of the high molecular weight polymers described herein approaches infinity. Thus, the molecular weight of a high molecular weight polymer can be a function of the mass and physical dimensions of the polymer being analyzed. For example, it can be assumed that an integral sample of melanoidin having a mass of 3 grams contains a single polymer molecule due to extensive crosslinking. Therefore, the molecular weight of the polymer is considered to be about 1.8 × 10 ²⁴ grams per mole (product of sample mass and Avogadro's number). High molecular weight polymers as used herein include polymers having a molecular weight on the order of between about 1 × 10 ⁵ to about 1 × 10 ²⁴ grams per mole.

  Without being limited to a particular theory, it is understood that the structure of a high molecular weight polymer will vary depending on the reactants and conditions at the time of preparation. High molecular weight polymers are also known to have a carbon to nitrogen ratio that increases with the temperature and time of heating. In addition, high molecular weight polymers have saturated, unsaturated, and aromatic characteristics. In one embodiment, the high molecular weight polymer had an unsaturation and aromaticity that increased with the temperature of heating (curing temperature) and time (curing time). The high molecular weight polymer also contained the sugar C-1, which was incorporated as a reactant in various structures within the polymer. High molecular weight polymers may contain carbonyl, carboxyl, amine, amide, pyrrole, indole, azomethine, ester, anhydride, ether, methyl, and / or hydroxyl groups. Depending on the complexity of the structure, infrared spectroscopy may be useful in identifying one or more of these functional groups. Although not classified as such herein, one of ordinary skill in the art will also appreciate that binders may be categorized according to the presence of particular bonds present, such as polyesters, polyethers, polyamides, and the like.

  Another approach that can characterize the binder is by analysis of gaseous compounds that are generated during the thermal decomposition of the cured binder. Gas pyrolysis of cured binders within the scope of the present disclosure includes the following compounds: 2-cyclopenten-1-one, 2,5-dimethyl-furan, furan, 3-methyl-2,5-furandione, phenol, 2 , 3-dimethyl-2-cyclopenten-1-one, 2-methylphenol, 4-methylphenol, 2,4-dimethyl-phenol, dimethylphthalate, octadecanoic acid, or erucylamide, about 0. 5 to about 15% (in relative peak areas). A pyrolysis gas chromatography mass spectrometry (Py GC-MS) fingerprint performed at 770 ° C. of a binder sample prepared using hexamethylene diamine as the polyamine component is composed of pyridine and pyrrole or pyridine derivatives ( The number of components that are methylpyridine, methylpyrrole, dimethylpyridine, dimethylpyrrole, ethylmethylpyrrole, and other pyrrole-related N-containing components) is shown. Another approach that can identify the binding agent is whether the solution (or extraction solution) containing the binding agent can reduce the Benedict reagent. In one embodiment, the solution in contact with the binding agent or aqueous extract thereof reduces the Benedict reagent.

  One aspect of the present disclosure is that the binders described herein are environmentally friendly. Along with ongoing government regulations, this disclosure describes binders that can be made formaldehyde-free. Furthermore, the chemistry described herein is essentially free of formaldehyde and phenol. In this sense, neither formaldehyde nor phenol is used as a reagent within the scope of this disclosure. Although either can be added to obtain a binder with potentially useful properties, one aspect of the present disclosure is a binder that can be made without both of these reagents. In another aspect, the binder composition of the present invention can be made without the use of volatile reactants. In one embodiment, both the nucleophile and the carbohydrate are non-volatile reactants. As used herein, a volatile reactant is one that has a vapor pressure greater than 10 kPa at 20 ° C. Similarly, non-volatile reactants used herein have a vapor pressure of less than about 10 kPa at 20 ° C. Specifically, by way of example, the binder of the present invention can be produced without adding ammonia or an ammonia releasing compound. In one embodiment, the nucleophile has a vapor pressure of less than about 0.5 kPa at 60 ° C.

  Another, environmentally friendly aspect of the present disclosure is that the primary reactant of the binder is a carbohydrate. Carbohydrates are considered renewable resources. However, the state of the art mainly uses petroleum-derived reactants to produce the binder composition. In another embodiment, the binder is made through a chemical reaction that can occur at a lower temperature than in the equivalent system described in the prior art. Thus, the curing furnace and manufacturing equipment can be operated at lower temperatures, saving valuable resources. In an alternative, related approach, the binder described herein cures more rapidly than the equivalent binder currently used when exposed to similar curing temperatures. Thus, with either approach, one aspect of the present disclosure provides for the carbon footprint of products formed using currently disclosed binders to be compared to equivalent binders made by state of the art, such as phenol. It can be significantly reduced compared to products based on formaldehyde.

  In addition to environmental benefits, the binder compositions of the present invention and materials made using them are made to have performance characteristics that are equal to or greater than equivalent binder systems, such as phenol formaldehyde binders. Can be done. In one aspect, the binder according to the present disclosure provides an article of sufficient tensile strength that is made using the binder that allows for punching, fabrication, lamination, and installation in OEM applications. In one aspect, the binder according to the present disclosure has a water hold-up property (weather resistance) equivalent to that of a phenol formaldehyde binder. Other performance characteristics that may be relevant to a particular application include product emissions, density, loss on ignition, thickness recovery, dust, tensile strength, breaking strength, durability of breaking strength, bond strength, water absorption, heat Includes surface performance, steel corrosivity, bending stiffness, stiffness, compression resistance, conditional compression resistance, compression modulus, conditional compression modulus, and ignition fumes. One aspect of the present disclosure is that the pH of the cured binder extract is essentially neutral, such as between 6 and 8. Another aspect of the present disclosure is that the binder of the present invention allows the production of products having related performance characteristics comparable to phenol formaldehyde binder compositions.

  Illustratively, in one aspect, the binder according to the invention of the present disclosure has the advantage of providing an essentially colorless aqueous extract. This feature of the present disclosure makes the binder desirable in applications such as ceiling tiles, furniture, or office panels where the finished product may come into contact with water. Cured products made using the binders of the present invention exhibit excellent resistance to discoloration or breathing after contact with moisture or water. Further, in such embodiments, water that contacts the binder does not leave a residual color on other articles or parts that may contact after contacting the binder. For example, in one embodiment, the binder may be used to bond glass fibers in office panel applications. Covering the bonded fiberglass composition may be a lightly colored fabric. In one embodiment, the water in contact with the glass fiber composition advantageously does not leave a colored residue on the fabric after the office panel is dried.

  In addition to performance characteristics, the manufacturing processes and methods involving currently disclosed binders have several unexpected advantages over the binders described above. In one aspect, as described above with respect to environmental benefits, the binder of the present invention can be produced without the use of highly volatile reactants. Therefore, the production release regulation is a regulation under a reduced burden. Furthermore, the reaction efficiency is higher because the loss of reactants due to vaporization is reduced. Thus, one aspect of the present disclosure is that the compounds used herein are substantially non-volatile, thus reducing the steps that must be taken to reduce undesirable emissions.

  According to another aspect, the reactants that react to form the binder react slowly enough so that a one-step / one-pot binder system can be used. According to this embodiment, the reactant compounds react sufficiently slowly so that they can be added to a single reactant solution and stored for a reasonable amount of time, while using a single distribution system to attach to the product. be able to. This is contrasted with binder systems that react at low temperatures to yield insoluble reaction products within the binder solution delivery system. As used herein, a reasonable time to store without substantial (> 5%) polymer precipitation is 2 weeks.

Another aspect of the present disclosure is that the binder does not react well at room temperature conditions that facilitate the one-pot approach, but the binder is sufficiently reactive at high temperatures and is very low and / or very Cures with a short cure residence time. In one aspect, the reduced cure temperature reduces the risk of the insulation product where flameless combustion occurs and / or causes a linefire. The very low temperature used herein is characterized as about 120 ° C. or less. The very short cure time used herein is about 4 minutes or less.

  In an exemplary embodiment, the binder composition includes an acid or acid salt to increase the shelf life of the uncured binder or binder solution. This acid is neither a reactant nor a catalyst, but it is used to slow down or inhibit the binder reactant from forming the binder while maintaining the binder solution or uncured binder under storage conditions. Can be included. For example, volatile acids or acid salts that slow or inhibit the curing reaction at ambient conditions may be included in the binder solution or uncured binder. However, the acid may be removed by heating the binder solution or uncured binder such that the acid is volatilized and the pH of the binder solution or uncured binder is increased. In one embodiment, the binder composition comprises an acid that extends shelf life. In another embodiment, the binder composition comprises an acid and nucleophile that extends shelf life in a molar ratio of about 1:20 to about 1: 1.

  Another aspect of the present disclosure is a binder having a cure rate, cycle time, and cure temperature that satisfies or exceeds the cure rate that equivalent phenol and formaldehyde type binders can exhibit within the scope of equivalent use. is there. In this regard, the binder of the present invention can be used as a direct replacement for phenol formaldehyde resin in applications that do not modify the equipment. Furthermore, the binder according to the invention makes it possible to modify the curing temperature and time so that both the reaction temperature and the curing time can be reduced. This reduction has the effect of reducing the energy consumption of the entire process, and this reduction reduces the environmental impact of product manufacture. Furthermore, the lower curing temperature has the additional effect of increasing the safety of the manufacturing process. Another effect of lower cure temperatures is to reduce the risk of flameless combustion or ignition.

  In the manufacture of insulating products, the heat released by the exothermic curing reaction can lead to self-heating of the product. Self-heating is typically not a problem as long as heat is dissipated from the product. However, if heat causes the product temperature to rise to the point where the oxidation process begins, self-heating can cause significant damage to the product. For example, flameless combustion or oxidation can occur when the temperature of the insulation product exceeds about 425 ° F. (210 ° C.). At these temperatures, the exothermic combustion or oxidation process promotes further self-heating and the binder can be destroyed. Further, the temperature can rise to a level where glass fiber melting or devitrification can occur. This not only detracts from the structure and value of the insulation product, but can also cause a fire disaster.

  Another aspect of the present disclosure is that the binder system is essentially non-corrosive, with or without the addition of corrosion inhibitors. Furthermore, the binder system does not require the addition of any organic acids, inorganic acids, and salts thereof as catalysts or active ingredients. Thus, one aspect of the binder of the present invention is that it can be made essentially free of acid. Furthermore, the binder may be produced under alkaline conditions as a whole. The term acid as used herein includes compounds that can be characterized primarily with respect to the acidic properties of the compound, such as polyprotic inorganic acids and polyprotic organic acids (eg, sulfuric acid and citric acid). . This aspect reduces manufacturing equipment wear and maintenance requirements and increases operator safety.

In an exemplary embodiment, the binder comprises a polymer product of a carbohydrate reactant and a nucleophile. As used herein, the term carbohydrate reactant refers to monosaccharides, disaccharides, polysaccharides, or their reaction products. In one embodiment, the carbohydrate reactant may be a reducing sugar. As used herein, a reducing sugar is one or more sugars that contain an aldehyde group, or one or more sugars that can be isomerized, ie tautomerized, to contain an aldehyde group. This group can be oxidized with, for example, Cu ⁺² to give a carboxylic acid. It is also understood that any such carbohydrate reactant may be optionally substituted with hydroxy, halo, alkyl, alkoxy, and the like. There are one or more chiral centers in any such carbohydrate reactant, and the possible optical isomers together at each chiral center are included in the invention described herein. Is further understood. In addition, various mixtures, including racemic mixtures, or other diastereomeric mixtures of various optical isomers of any such carbohydrate reactant, as well as various geometric isomers thereof, are described herein. It is similarly understood that it may be used in one or more of the described embodiments. Non-reducing sugars such as sucrose may not be preferred, but nevertheless the non-reducing sugars may be useful within the scope of this disclosure by in-situ conversion to reducing sugars (ie, converted from sucrose. Conversion to sugar is a method known in the art). It is further understood that monosaccharides, disaccharides, or polysaccharides may partially react with the precursor such that a carbohydrate reaction product is formed. Nucleophiles such that the carbohydrate reaction product is derived from a monosaccharide, disaccharide, or polysaccharide and a reaction product similar to the reaction product of a monosaccharide, disaccharide, or polysaccharide and a nucleophile is formed. As long as a similar reactivity with is maintained, the carbohydrate reaction product is within the scope of the term carbohydrate reactant.

  In one aspect, any carbohydrate reactant should be sufficiently non-volatile to maximize its ability to remain available for reaction with the nucleophile. The carbohydrate reactant may be a monosaccharide that is in its aldose or ketose form including triose, tetrose, pentose, hexose, or heptose; or a polysaccharide; or a combination thereof. For example, if triose acts as a carbohydrate reactant or is used in combination with other reducing sugars and / or polysaccharides, aldotriose sugars or ketotriose sugars such as glyceraldehyde and dihydroxyacetone may be utilized, respectively. . When tetrose acts as a carbohydrate reactant or is used in combination with other reducing and / or polysaccharides, aldetetrose sugars such as erythrose and threose; and ketotetrose sugars such as erythrulose may be utilized. Aldopentose sugars such as ribose, arabinose, xylose, and lyxose; and ribulose, arabulose, xylulose, and lyxulose when pentose acts as a carbohydrate reactant or is used in combination with other reducing and / or polysaccharides Ketopentose sugars such as may be used. When hexose acts as a carbohydrate reactant or is used in combination with other reducing sugars and / or polysaccharides, such as glucose (ie, dextrose), mannose, galactose, allose, altrose, talose, gulose, and idose Aldohexose sugars; and ketohexose sugars such as fructose, psicose, sorbose, and tagatose may be utilized. If heptose acts as a carbohydrate reactant or is used in combination with other reducing sugars and / or polysaccharides, a ketoheptose sugar such as cedoheptulose may be utilized. It is contemplated that other stereoisomers of such carbohydrate reactants that are not known to occur in nature are also useful in preparing the binder compositions described herein. In one embodiment, the carbohydrate reactant is high fructose corn syrup.

  In an exemplary embodiment, the carbohydrate reactant is a polysaccharide. In one embodiment, the carbohydrate reactant is a polysaccharide having a low degree of polymerization. In one embodiment, the polysaccharide is molasses, starch, cellulose hydrolysate, or a mixture thereof. In one embodiment, the carbohydrate reactant is a starch hydrolyzate, maltodextrin, or a mixture thereof. Although higher degrees of polymerization of carbohydrates may be undesirable, such carbohydrates are nevertheless considered useful within the scope of this disclosure by in-situ depolymerization (ie, high temperature ammonia treatment). Is a method known in the art).

  In addition, the carbohydrate reactant may be used in combination with a non-carbohydrate polyhydroxy reactant. Examples of non-carbohydrate polyhydroxyl reactants that can be used in combination with carbohydrate reactants include trimethylolpropane, glycerol, pentaerythritol, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, fully hydrolyzed Polyvinyl acetate, and mixtures thereof, but are not limited thereto. In one aspect, the non-carbohydrate polyhydroxy reactant is sufficiently non-volatile to maximize its ability to remain available for reaction with monomeric or polymeric polyamines. It will be appreciated that the hydrophobicity of the non-carbohydrate polyhydroxy reactant may be a factor in determining the physical properties of a binder prepared as described herein.

  A nucleophile as used herein is a reagent that forms a bond with its reaction partner (electrophile) by donating both binding electrons. As used herein, an electrophile is a reagent that forms a bond with a reaction partner (nucleophile) by accepting both binding electrons from the reaction partner. Illustratively, the electrophile is a carbohydrate described herein. Specifically, the electrophile group is a carbon associated with an aldose form or ketose form of a carbohydrate. For example, C-1 in glucose is positive due to aldose functionality and reacts with the nucleophiles of the present disclosure. In another example, fructose C-2 is positively charged with ketose functionality and reacts with the nucleophiles of the present disclosure. Although carbohydrates have been described as electrophiles in their initial interaction with nucleophiles, those skilled in the art will appreciate that carbohydrates are not limited to acting only as electrophiles within the range of possible reactions. Will. For example, the hydroxyl group of a carbohydrate can act as a nucleophile depending on the presence of a reactive nucleophile. In addition, the initial reaction between the nucleophile and the carbohydrate can accurately classify the carbohydrate as an electrophile, but the product of that reaction is both a nucleophile and an electrophile in further reactions. Functionality can be demonstrated.

  In an exemplary embodiment, the nucleophile is sufficient to react with a carbohydrate that is in its aldose form or ketose form in a solution having the pH described herein and the temperature described herein. It is nucleophilic. In one embodiment, the nucleophile includes a cation stabilizing moiety. As used herein, a cation stabilizing moiety is a chemical group on a nucleophile that stabilizes cations formed by nucleophilic attack. For example, one nucleophile that is within the scope of this disclosure is a diamine. The nucleophilic attack of the carbonyl by the primary amine forms a Schiff base cation. The first amine of the diamine acts as a nucleophile, while the second amine acts as a cation stabilizing moiety when stabilizing the Schiff base cation. It is known that the further rearrangement of the cation from the Schiff base to the enol or keto form proceeds spontaneously. The cation formed by nucleophilic attack is similarly stabilized by the structure of the nucleophile (as is the Schiff base). In another aspect, the structure of the nucleophile accelerates the rearrangement by stabilizing the positive charge acquired while the compound is in the form of a cation formed by nucleophilic attack.

  It has been discovered that this spontaneous reaction is further facilitated by dehydration as the rate increases in the dehydrated sample. The importance of the stabilizing moiety would not have been discussed in the prior art within the scope of this application since the enhanced effect of using the nucleophiles of the present disclosure has not been previously disclosed. Accordingly, one aspect of the present disclosure is a type of nucleophile that provides stability to the cation of the nucleophile base during subsequent rearrangements. In another aspect, the nucleophile is of the type that provides stability to the cation of the nucleophile base during subsequent rearrangements while substantially dry.

In exemplary embodiments, the nucleophile is R ₁ -QR ₂ , wherein Q is alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, and the alkyl, cycloalkyl, heteroalkyl, Each cycloheteroalkyl is optionally substituted, R ₁ is a nucleophilic moiety and R ₂ is a stabilizing moiety. In one embodiment, R ₁ is selected from the group consisting of amine, azide, cyanate, isocyanate, thiol, disulfide, thiocyanate, halogen, haloformyl, carboxyl, carboxylate, hydroxyl, and alkoxide. In another embodiment, R ₂ is selected from the group consisting of amine, amide, imine, imide, nitro, nitrate, pyridine, phosphate, phosphono, hydroxyl, hydrogen, sulfono, sulfo, sulfinyl, and sulfhydryl (thiol). .

In one embodiment, the nucleophile is a primary amine. As used herein, a primary amine is an organic compound having one or more primary amine groups. Within the scope of the term primary amine, in order to produce compounds having one or more primary amine groups.
There are compounds that can be modified in situ or isomerized. In one embodiment, the primary amine may be a molecule having the formula H ₂ NQR, where Q is alkyl, cycloalkyl, heteroalkyl, or cycloheteroalkyl, and Each of alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl may be optionally substituted, and R is amine, amide, imine, imide, nitro, nitrate, pyridine, phosphate, phosphono, hydroxyl, hydrogen, sulfono A cation stabilizing moiety selected from the group consisting of, sulfo, sulfinyl, and sulfhydryl (thiol).

In one _embodiment, Q is alkyl selected from the group consisting of C 2 _{-C 24.} In another embodiment, Q is alkyl selected from the group consisting of C ₂ -C _8. In another embodiment, Q is alkyl selected from the group consisting of C ₃ -C _7. In yet another embodiment, Q is C ₆ alkyl. In one embodiment, Q is selected from the group consisting of cyclohexyl, cyclopentyl, or cyclobutyl. In another embodiment, Q is benzyl. In one embodiment, R ₁ -QR ₂ is 2-[(2-aminoethyl) amino] ethanol. In another embodiment of R _{1 -Q-R 2,} each of _{R 1} and _{R 2} is a thiol.

In one embodiment, R ₁ is an amine. In further embodiments described above, R ₂ is an amine, amide, imine, or imide. In further embodiments described above, R ₂ is an amine.

The term “alkyl” as used herein includes an optionally branched chain of carbon atoms. The terms “alkenyl” and “alkynyl” as used herein include an optionally branched chain of carbon atoms, each containing at least one double or triple bond. It is also understood that alkynyl may contain one or more double bonds. It is further advantageous that the alkyl is of a limited length including C ₁ -C ₂₄ , C ₁ -C ₁₂ , C ₁ -C ₈ , C ₁ -C ₆ , and C ₁ -C _4. Understood. Alkenyl and / or alkynyl, respectively, _{preferably, C 2 ~C 24, C 2} ~C 12, C 2 ~C 8, C 2 ~C 6, and _C 2 -C length limited, including ₄ It is further understood that this may be true. Shorter alkyl, alkenyl, and / or alkynyl groups may not significantly increase the hydrophilicity of the compound and thus will have different reactivities to carbohydrate reactants and solubility in binder solutions, As understood herein.

The term “cycloalkyl” as used herein includes an optionally branched chain of carbon atoms, at least a portion of which is cyclic. It is understood that cycloalkylalkyl is a subset of cycloalkyl. It will be appreciated that the cycloalkyl may be polycyclic. Exemplary cycloalkyls include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, 2-methylcyclopropyl, cyclopentyleth-2-yl, adamantyl, and the like. The term “cycloalkenyl” as used herein includes an optionally branched chain of carbon atoms, including at least one double bond, at least a portion of which is cyclic. It is understood that one or more double bonds may be present in the cyclic part of cycloalkenyl and / or the non-cyclic part of cycloalkenyl. It is understood that cycloalkenylalkyl and cycloalkylalkenyl are each a subset of cycloalkenyl. It will be appreciated that the cycloalkyl may be polycyclic. Exemplary cycloalkenyl includes, but is not limited to, cyclopentenyl, cyclohexylethen-2-yl, cycloheptenylpropenyl, and the like. Chains form a cycloalkyl and / or _{cycloalkenyl, C 3 ~C 24, C 3} ~C 12, C 3 ~C 8, C 3 ~C 6, and _C 5 -C length limited, including ₆ It is further understood that this is advantageous. It is understood herein that each shorter alkyl and / or alkenyl chain forming a cycloalkyl and / or cycloalkenyl may not significantly increase the lipophilicity of the compound and therefore will have different behavior. Is done.

  The term “heteroalkyl” as used herein includes an optionally branched chain of atoms containing both carbon and at least one heteroatom. Exemplary heteroatoms include nitrogen, oxygen, and sulfur. In some variations, exemplary heteroatoms also include phosphorus and selenium. The term “cycloheteroalkyl” as used herein, including heterocyclyl and heterocycle, includes and includes a chain of atoms including both carbon and at least one heteroatom (eg, heteroalkyl, etc.). Are optionally branched and at least a portion of the chain is cyclic. Exemplary heteroatoms include nitrogen, oxygen, and sulfur. In some variations, exemplary heteroatoms also include phosphorus and selenium. Exemplary cycloheteroalkyls include, but are not limited to, tetrahydrofuryl, pyrrolidinyl, tetrahydropyranyl, piperidinyl, morpholinyl, piperazinyl, homopiperazinyl, quinuclidinyl, and the like.

  The term “optionally substituted” as used herein includes the replacement of a hydrogen atom with another functional group on an optionally substituted radical. Such other functional groups include, by way of example, amino, hydroxyl, halo, thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, nitro, sulfonic acid and their derivatives, carboxylic acids and these However, it is not limited to these. By way of example, any of amino, hydroxyl, thiol, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, and / or sulfonic acid are optionally substituted.

  In exemplary embodiments, the primary polyamine is a diamine, triamine, tetraamine, or pentamine. In one embodiment, the nucleophile is a triamine selected from diethylenetriamine, 1-piperazineethanamine, or bis (hexamethylene) triamine. In another embodiment, the polyamine is tetramine, such as triethylenetetramine. In another embodiment, the polyamine is pentamine, such as tetraethylenepentamine.

  One embodiment of the nucleophile is one that may have low steric hindrance. For example, Q is selected such that the nucleophile has low steric hindrance. For example, if Q is essentially linear and has a length of at least 3 atoms, the nucleophilic moiety and stabilizing moiety are sufficiently spaced so that the nucleophile can react with the electrophile. doing.

  Without being limited to a particular theory, the stabilizing moiety is so called because it can stabilize the reaction intermediates described herein. However, in another aspect of the present disclosure, the stabilizing moiety may serve as a reactant within the scope of the present disclosure. Thus, the rearrangement product present after the reaction between the nucleophilic moiety and the carbohydrate can convert or return the stabilizing moiety to a group that can react or react with another carbohydrate. Thus, the stabilizing moiety can be converted or returned to the form of a nucleophilic moiety and can react with the carbohydrate accordingly.

In an exemplary embodiment, the Q group described herein separates the two groups such that R ₁ and R ₂ are essentially unaffected by the chemistry that occurs at other positions. Can work like. Thus, the Q group may or may not work within the capacity of the stabilizing moiety. According to this theory, the benefits gained through the use of bifunctional nucleophiles are mainly due to the fact that a single bifunctional compound can form a bridge between two carbohydrate compounds. To do. The two functional groups are linked through the Q group by reaction of both R ₁ and R ₂ , resulting in a higher molecular weight product than if R ₁ and R ₂ were not bonded through the Q group. can get. Thus, R ₁ and R ₂ are amine, azide, cyanate, isocyanate, thiol, disulfide, thiocyanate, halogen, haloformyl, carboxyl, carboxylate, hydroxyl, alkoxide, amide, imine, imide, nitro, nitrate, pyridine, phosphate, It can be selected from the group consisting of phosphono, hydroxyl, hydrogen, sulfono, sulfo, sulfinyl, and sulfhydryl (thiol).

In an exemplary embodiment, the Q group is of the type that allows chemical communication between R ₁ and R ₂ . For example, Q can allow chemical communication by allowing resonance and polarity shift from R ₁ to R ₂ . In other embodiments, Q may be of a length such that a reaction at either R ₁ and R ₂ causes a change in the electron distribution at the other group (R ₁ or R ₂ ). . In one embodiment, the nucleophile comprises a stabilizing moiety and a nucleophilic moiety. In one embodiment, the nucleophilic moiety is selected from the group consisting of amines, azides, cyanates, isocyanates, thiols, disulfides, thiocyanates, halogens, haloformyls, carboxyls, carboxylates, hydroxyls, and alkoxides. In another embodiment, the cation stabilizing moiety is from the group consisting of amine, amide, imine, imide, nitro, nitrate, pyridine, phosphate, phosphono, hydroxyl, hydrogen, sulfono, sulfo, sulfinyl, and sulfhydryl (thiol). Selected.

  In one embodiment, the nucleophile may comprise a polymeric polyamine. For example, polymeric polyamines within the scope of this disclosure include chitosan, polylysine, polyethyleneimine, poly (N-vinyl-N-methylamine), polyaminostyrene, and polyvinylamine. In one embodiment, the polyamine comprises polyvinylamine. As used herein, polyvinylamine can be a homopolymer or a copolymer.

While not being limited to a particular theory, one aspect of the present disclosure is a Maillard reactant in which primary amines and carbohydrate reactants react to form a melanoidin product. FIG. 1 shows a schematic of the Maillard reaction that ultimately produces melanoidin. In its early stages, the Maillard reaction requires a carbohydrate reactant, such as a reducing sugar (note that the carbohydrate reactant is derived from a substance capable of producing a reducing sugar under Maillard reaction conditions. ). The reaction also includes condensation of a carbohydrate reactant (eg, reducing sugar) with an amine reactant, ie, a compound having an amino group. In other words, the carbohydrate reactant and amine reactant are melanoidin reactants for the Maillard reaction. Condensation of these two components produces an N-substituted glycosylamine. For a more detailed description of the Maillard reaction, see Hodge, JEChemistry of Browning Reactions, the disclosure of which is incorporated herein by reference.
in Model Systems J. Agric. Food Chem. 1953, 1 pp. 928-943. The literature on the Maillard reaction focuses on melanoidins produced from amino acids. The present disclosure can be distinguished from these references in that nucleophiles within the scope of the present disclosure also include a stabilizing moiety. Common amino acids considered within the scope of this disclosure include asparagine, glutamine, histidine, lysine, and arginine.

  Without being bound by theory, a more specific description of the covalent reaction between the nucleophile and the carbohydrate reactant is described. As described herein, the reaction pathway of the present invention is clearly different from that taught in the prior art for the following reasons: (1) The reaction of the present invention is completely basic pH (2) the nucleophile is bifunctional with a nucleophilic moiety and a stabilizing moiety, and (3) the nucleophile reacts through its bifunctionality or another unrecognized phenomenon. Exhibits a lower activation energy within the range of, resulting in an unexpected increase in reaction rate and / or a decrease in temperature at which the reaction proceeds.

  In an exemplary embodiment, the first step in forming a high molecular weight polymer from a nucleophile and a carbohydrate reactant is the condensation of the carbohydrate reactant with the nucleophile. The evidence indicates that the conditions described herein are particularly suitable for driving the reaction to completion. First, it is believed that the alkalinity of the binder solution drives the condensation. For example, nucleophiles such as sugars and amines have been shown to turn brown in aqueous solution in proportion to the base strength of the amine used or the pH of the solution. In this example, the N-substituted glycosylamine is believed to remain undissociated in aqueous solution to a significant extent. Therefore, irreversible deformations experienced by undissociated molecules must be considered. Although the condensation reaction is known to be reversible, the inventors have discovered that this reaction can be further driven to completion according to Le Chatelier's principle by parallel dehydration of the binder solution. . Thus, it was first demonstrated that the primary component of an uncured binder composition is a condensation product of a nucleophile and a carbohydrate.

  The second step in the conversion of the binder reactant to the high molecular weight polymer product can be rearrangement. An exemplary dislocation is shown as a schematic diagram of the Amadori dislocation of FIG. Referring to FIG. 2, a representative amine N-glycosyl derivative is in equilibrium with a Schiff base cation. This equilibrium favors N-glycosylamine, but it is known that further rearrangement of the Schiff base cation from the enolic or keto form proceeds spontaneously. It was discovered that this spontaneous reaction was further facilitated by dehydration as the rate increased in the dehydrated sample. One aspect of the present disclosure is that the structure of the nucleophile specifically accelerates this rearrangement by stabilizing the positive charge acquired while the compound is in the form of a Schiff base cation. This stabilizing effect is considered not discussed in the prior art or literature, since the enhanced effect of using such nucleophiles within the scope of this disclosure has not been previously disclosed. Thus, one aspect of the present disclosure is that the nucleophile is of the type that provides stability to the cationic base during rearrangement. In another aspect, the nucleophile is of the type that provides stability to the cationic base during rearrangement while in the substantially dry state.

  Another aspect of the present disclosure is that the carbohydrate structure is also thought to affect dislocation kinetics. Specifically, it is known that when the C-2 hydroxyl of a crystalline N-substituted glycosylamine is not substituted, the compound slowly transformed into a rearrangement product during storage. However, when the C-2 hydroxyl was substituted, the rearrangement was substantially inhibited. Accordingly, one aspect of the present disclosure is that the carbohydrate of the present disclosure is not substituted with a hydroxyl adjacent to a ketone or aldehyde.

  In an exemplary embodiment, the molar ratio of carbohydrate reactant to nucleophile is in the range of about 1: 1 to about 30: 1. In another embodiment, the molar ratio of carbohydrate reactant to nucleophile is in the range of about 2: 1 to about 10: 1. In yet another embodiment, the molar ratio of carbohydrate reactant to nucleophile is in the range of about 3: 1 to about 6: 1. According to one aspect, the cure rate is a function of the molar ratio of carbohydrate reactant to primary polyamine. This function demonstrated that the cure rate increased as the ratio decreased, thus shortening the cure time. Thus, one aspect of the present disclosure is that the cure time is directly related to the molar ratio of carbohydrate reactant to polyamine if other parameters are maintained equal. In another aspect, the binder cure time is reduced to the cure time of an equivalent phenol formaldehyde binder composition when the molar ratio of carbohydrate reactant to nucleophile is equal to about 6: 1. Accordingly, in one embodiment, a binder according to the present disclosure exceeds an equivalent phenol formaldehyde binder system when the molar ratio of carbohydrate reactant to nucleophile is in the range of about 2: 1 to about 6: 1. Has a cure rate.

  Another aspect of the reactions described herein is that initially the aqueous reactant solution (which may be dehydrated and used as a binder) has an alkaline pH. One aspect of the present disclosure is that alkaline binder solutions are less corrosive to metals than acidic solutions. Accordingly, one feature of the present disclosure that overcomes a substantial barrier to industry is that the binder described herein produces a material that includes the binder of the present invention due to the alkaline binder composition. It has low corrosiveness to manufacturing equipment that may be used to do so. One distinguishing feature of the present disclosure over other recently described carbohydrate binder systems (eg, US 2007/0027283) is that the reaction does not necessarily proceed through the acidic pathway. It is. Rather, one aspect of the present disclosure is that the uncured binder can have an alkaline pH throughout the course of the chemical reaction that results in the formation of the cured binder. Uncured binders therefore pose no risk of corrosion throughout their use and storage. In an exemplary embodiment, the aqueous extract of the cured binder has a pH in the range of about 5 to about 9. Furthermore, the aqueous extract of the polymer product is essentially colorless.

  In an exemplary embodiment, a method of making an object assembly bonded with a polymer binder comprises preparing a solution containing a reactant and a solvent to produce a polymer binder, the reactant Including a carbohydrate reactant and a nucleophile; placing the solution on the object assembly; evaporating the solvent to form an uncured product; and the uncured product Subjecting the carbohydrate reactant and nucleophile to a condition to polymerize to form a polymeric binder.

  In an exemplary embodiment, the object assembly includes insulating fibers. In one embodiment, a fiber insulation product is described that includes an insulation fiber and a binder. As used herein, the term “insulating fiber” refers to a heat resistant fiber suitable for withstanding high temperatures. Examples of such fibers include mineral fibers (glass fibers, slag wool fibers, and rock wool fibers), aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, certain polyester fibers, and rayon fibers. However, it is not limited to these. Illustratively, such fibers are substantially unaffected by exposure to temperatures above about 120 ° C. In one embodiment, the insulating fiber is a glass fiber. In yet another embodiment, the mineral fibers are present in the range of about 70% to about 99% by weight.

In an exemplary embodiment, the object assembly includes cellulose fibers. For example, the cellulose fibers may be wood chips, sawdust, wood pulp, or crushed wood. In yet another embodiment, the cellulose fibers may be other natural fibers such as jute, flax, hemp, and straw. The binders disclosed herein may be used in place of the binders described in published PCT application WO 2008/0889847, which is hereby incorporated by reference in its entirety. In one embodiment, a composite wood board comprising wood particles and a binder is disclosed. In another embodiment, the composite wood board is formaldehyde free. In one embodiment, the composite wood board has a thickness ranging nominal to 6mm super 13 mm, elastic modulus of at least about 1050N / mm ² (MOE), at least about 7N / mm ² bending strength (MOR), and It has an internal bond strength (IB) of at least 0.20 N / mm ² . In another embodiment, the composite wood board has a thickness ranging nominal to 6mm super 13 mm, at least about 12.5 N / mm ² Bending strength (MOR) and at least an internal bond strength of 0.28 N / mm ² ( IB). In another embodiment, the composite wood board has a thickness ranging nominal to 6mm super 13 mm, elastic modulus of at least about 1800N / mm ² (MOE), at least about 13N / mm ² in bending strength (MOR), and having at least an internal bond strength of 0.40 N / mm ² a (IB). In another embodiment, the composite wood board has a modulus of elasticity (MOE) of at least about 1800 N / mm ² . In another embodiment, the composite wood board has a modulus of elasticity (MOE) of at least about 2500 N / mm ² . In another embodiment, the composite wood board has a flexural strength (MOR) of at least about 14 N / mm ² . In yet another embodiment, the composite wood board has a bending strength (MOR) of at least about 18 N / mm ² . In one embodiment, the composite wood board has an internal bond strength (IB) of at least 0.28 N / mm ² . In yet another embodiment, the composite wood board has an internal bond strength (IB) of at least 0.4 N / mm ² . In yet another embodiment, the composite wood board swells at about 12% or less when measured for thickness change after 24 hours in 20 ° C. water. In another embodiment, the composite wood board has a water absorption of about 40% or less after 24 hours in 20 ° C. water.

  In exemplary embodiments, the composite wood board is a wood particle board, an oriented strand board, or a medium density fiber board. In one embodiment, the binder comprises about 8% to about 18% by weight of the composite wood board (weight of dry resin relative to the weight of dry wood particles). In another embodiment, the composite wood board further comprises a wax. In yet another embodiment, the composite wood board comprises from about 0.1% to about 2% wax by weight of the composite wood board. In an exemplary embodiment, a method of making an assembly of objects bonded with a polymer binder comprises a certain amount of carbohydrate reactant and a certain amount of nucleophile in a molar ratio of about 2: 1 to about 10: A step of preparing a solution by adding to be in the range of 1 may be further included. In one embodiment, preparing the solution includes adding a carbohydrate reactant and a polyamine to the aqueous solution. In another embodiment, preparing the solution includes adjusting the pH of the solution within the range of about 8 to about 12. In yet another embodiment, the method of making an object assembly bonded with a polymeric binder may further comprise the step of packaging the uncured product into a packaging material suitable for storage.

In an exemplary embodiment, the present disclosure relates to a composition comprising an object assembly and a binder, the binder comprising a polymer product of a reaction between a carbohydrate reactant and a nucleophile, and a polymer The product is substantially water insoluble. In one embodiment, the object assembly includes mineral fibers, aramid fibers, ceramic fibers, metal fibers, carbon fibers, polyimide fibers, polyester fibers, rayon fibers, or cellulose fibers. For example, the cellulose fibers may include wood chips, sawdust, wood pulp, and / or crushed wood. In one embodiment, the object assembly includes sand or other inorganic particulate material. In one embodiment, the object assembly is fine coal particles. In one embodiment, the carbohydrate reactant is selected from the group consisting of dextrose, xylose, fructose, dihydroxyacetone, and mixtures thereof. In one embodiment, the nucleophile is R 1 _{-Q-R 2,} wherein, Q is an alkyl, cycloalkyl, heteroalkyl or cycloheteroalkyl, said alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl Each heteroalkyl is optionally substituted, R ₁ is a nucleophilic moiety and R ₂ is a stabilizing moiety.

  In another embodiment, the composition further comprises a silicon-containing compound. In one embodiment, the silicon-containing compound is a functionalized silyl ether or a functionalized alkyl silyl ether, such as an amino functionalized alkyl silyl ether. For example, in one embodiment, the silicon-containing compound may be γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or aminoethylaminopropyltrimethoxysilane, or a mixture thereof. In another embodiment, the silicon-containing compound may be an amino functional oligomeric siloxane. In another embodiment, the composition is a corrosion selected from the group consisting of dust control oil, monoammonium phosphate, sodium metasilicate pentahydrate, melamine, tin (II) oxalate, and methyl hydrogen silicone fluid emulsion. Contains inhibitor.

  In another exemplary embodiment, the binder may be placed on the fiber assembly, substantially dehydrated, packaged, then stored or sold to another party. An uncured product sold to another party for use in a further manufacturing process may be referred to as a “shipping uncured product”. Uncured products stored for use in further manufacturing processes may be referred to as “plant uncured products”. When this type of product is sold or stored, it is packaged in a suitable container or bag.

  In an exemplary embodiment, the packaged uncured fiber product comprises an uncured binder composition and a fiber assembly, (i) the uncured binder composition contacts the fiber assembly, The uncured binder composition that hardens the fiber assembly and is in contact with the fiber assembly is packaged in a suitable packaging material. In one embodiment, the amount of moisture in the uncured binder composition may range from about 1% to about 15% by weight relative to the total weight of the product. In yet another embodiment, a suitable packaging material maintains the amount of moisture in the uncured binder composition within about 20% of the original moisture level over one week at ambient temperature and pressure. May be possible. In one embodiment, the packaged uncured fiber product is from about 3% to about 30% by weight relative to the weight of the packaged uncured fiber product without considering the weight of a suitable packaging material. Contains an uncured binder composition. In one embodiment, the packaged uncured fiber product comprises about 60 to about 97% by weight fiber, based on the weight of the packaged uncured fiber insulation product, without considering the weight of a suitable packaging material. including.

  One aspect of the present disclosure is that the binders described herein are unexpectedly useful in shipping uncured applications and plant uncured applications. Specifically, the shipping uncured product and the plant uncured product are provided with an uncured binder so that curing can occur later elsewhere. In the case of uncured products for shipping, the curing temperature and time are very important product properties for the customer. Specifically, the curing temperature must be low enough so that the product can be cured using the customer's existing equipment. Furthermore, the curing time must be sufficiently short so that the cycle time for curing the product remains short. In this industry, manufacturing equipment and acceptable cycle times have been established for uncured products including phenol formaldehyde type resins. Thus, a sufficiently low cure temperature is a cure temperature suitable for curing an equivalent phenol formaldehyde type product. Similarly, a sufficiently short cycle time is the cycle time which is the usual procedure for curing comparable phenol formaldehyde type products. One skilled in the art will appreciate that neither a cure time nor a cure temperature can be described as a definite amount, because a particular application can have dramatically different parameters. However, the cure time and cure temperature of the model system should provide sufficiently representative information on the kinetics of the underlying chemical cure reaction so that reliable predictions of binder performance in various applications can be made. Is fully understood.

  In an exemplary embodiment, the curing time and curing temperature of the binder is less than or equal to the equivalent phenol formaldehyde binder composition. In one embodiment, the curing time of the binder is less than the curing time of an equivalent phenol formaldehyde binder composition. In another embodiment, the curing temperature of the binder is less than the curing temperature of an equivalent phenol formaldehyde binder composition. The equivalent phenol formaldehyde binder composition used herein is similar to that described in US Pat. No. 6,638,882, which is incorporated herein by reference in its entirety.

  As discussed below, various additives can be incorporated into the binder composition. These additives provide additional desired characteristics to the binder of the present invention. For example, the binder may include a silicon-containing coupling agent. Many silicon-containing coupling agents are commercially available from Dow-Corning Corporation, Evonik Industries, and Momentive Performance Materials. Illustratively, silicon-containing coupling agents include compounds such as silyl ethers and alkyl silyl ethers, each of which may be optionally substituted with halogen, alkoxy, amino, and the like. . In one variation, the silicon-containing compound is γ-aminopropyltriethoxysilane (SILQUEST A-1101; Momentive Performance Materials, Corporate Headquarters: 22 Corporate Woods Boulevard, Albany, NY, 122122 USA). In another variation, the silicon-containing compound is an amino-substituted silane, such as aminoethylaminopropyltrimethoxysilane (Dow Z-6020; Dow Chemical, Midland, MI; USA). In another variation, the silicon-containing compound is γ-glycidoxypropyltrimethoxysilane (SILQUEST A-187; Momentive). In yet another variation, the silicon-containing compound is an amino-functional oligomeric siloxane (HYDROSIL 2627, Evonik Industries, 379 Interface Pkwy, Parsippany, NJ 07054).

  The silicon-containing coupling agent is about 0.1 percent to about 1 percent by weight based on the dissolved binder solids (ie, about 0.05% to about 3 percent based on the weight of solids added to the aqueous solution). %) Is typically present in the binder. In one application, one or more of these silicon-containing compounds can be added to the aqueous binder solution. A binder is then attached to the material to be bonded. Thereafter, the binder may be cured if desired. These silicone-containing compounds enhance the ability of the binder to adhere to objects (such as glass fibers) on which the binder is placed. By increasing the ability of the binder to adhere to an object, for example, the ability to generate or promote agglomeration in uncombined or loosely combined material (s) is improved.

  In another exemplary embodiment, the binder of the present invention may include one or more corrosion inhibitors. These corrosion inhibitors prevent or inhibit the erosion or wear of substances such as metals caused by chemical degradation caused by acids. When a corrosion inhibitor is included in the binder of the present invention, the corrosivity of the binder is reduced compared to the corrosivity of the binder in the absence of the inhibitor. In one embodiment, these corrosion inhibitors can be utilized to reduce the corrosivity of the glass fiber-containing compositions described herein. Illustratively, the corrosion inhibitors include the following materials: dust control oil, or monoammonium phosphate, sodium metasilicate pentahydrate, melamine, tin (II) oxalate, and / or methyl hydrogen silicone fluid emulsion. 1 type or multiple types of are included. When included in the binder of the present invention, the corrosion inhibitor is typically present in the binder in the range of about 0.5 weight percent to about 2 weight percent based on dissolved binder solids. One aspect of the present disclosure is that the need for a corrosion inhibitor additive is greatly reduced by the alkaline and substantially dehydrated uncured binder of the binder solution. In one embodiment, the binder does not include a corrosion inhibitor and the corrosivity of the binder solution is within an acceptable range.

  In an exemplary embodiment, the binder may further include a non-aqueous humidifier. The non-aqueous humidifier may contain one or more polyethers. For example, the non-aqueous humidifier may include an ethylene oxide or propylene oxide condensate having a linear and / or branched alkyl group and an alkaryl group. In one embodiment, the non-aqueous humidifier includes polyethylene glycol, polypropylene glycol ether, thioether, polyoxyalkylene glycol (eg, Jeffox TP400®), dipropylene glycol, and / or polypropylene glycol (eg, Pluriol P425). (Registered trademark) or Pluriol 2000 (registered trademark)). In one embodiment, the non-aqueous humidifier comprises polyoxyalkylene glycol or polypropylene glycol. In another embodiment, the non-aqueous humidifier comprises a compound based on a polyhydroxy compound (eg, a partially or fully esterified polyhydroxy compound). In another embodiment, the non-aqueous humidifier comprises polyhydroxy based on glycerin, propylene glycol, ethylene glycol, glyceryl acetate, sorbitol, xylitol, or maltitol.

  In another embodiment, the non-aqueous humidifier has tetrahydrofuran, caprolactone, and / or an alkyl group containing from about 7 to about 18 carbon atoms and from about 4 to about 240 ethyleneoxy units. Includes other compounds with multiple hydroxyl groups based on alkylphenoxypoly (ethyleneoxy) ethanol. For example, the non-aqueous humidifier may include heptylphenoxypoly (ethyleneoxy) ethanol and / or nonylphenoxypoly (ethyleneoxy) ethanol. In another embodiment, the non-aqueous humidifier comprises a polyoxyalkylene derivative of hexitol, such as sorbitan, sorbide, mannitan, and / or mannide. In yet another embodiment, the non-aqueous humidifier includes sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, and / or polyoxyalkylene derivatives of sorbitan trioleate, etc. The partial long chain fatty acid ester may be contained.

  In an exemplary embodiment, the non-aqueous humidifier comprises a condensate of ethylene oxide and a hydrophobic base that is formed by condensing propylene oxide and propylene glycol. In one embodiment, the non-aqueous humidifier condenses ethylene oxide with a higher alkyl mercaptan (eg, nonyl, dodecyl, tetradecyl mercaptan, or an alkylthiophenol having about 6 to about 15 carbon atoms in the alkyl group). A sulfur-containing condensate such as a sulfur-containing condensate prepared by In another embodiment, the non-aqueous humidifier comprises an ethylene oxide derivative of a long chain carboxylic acid, such as lauric acid, myristic acid, palmitic acid, or oleic acid. In yet another embodiment, the non-aqueous humidifier comprises an ethylene oxide derivative of a long chain alcohol such as octyl, decyl, lauryl, or cetyl alcohol. In another embodiment, the non-aqueous humidifier comprises an ethylene oxide / tetrahydrofuran copolymer or an ethylene oxide / propylene oxide copolymer.

  The following examples provide further details for specific embodiments. These examples are provided for illustrative purposes only, and are not to be construed as limiting the invention or the concepts of the invention in any way to any particular physical configuration.

(Example 1)
A solution prepared by dissolving 50 g (0.278 mol) of dextrose and 50 g (0.431 mol) of hexamethylenediamine in 566.6 g of deionized water (15% solid solution, pH 11.9) was heated to the boiling point of the solution. A brownish water insoluble polymer was observed as a precipitate in the reaction vessel.

(Example 2)
From the above solution (15% solid solution, pH 11.9) in which 50 g (0.278 mol) of dextrose and 50 g (0.431 mol) of hexamethylenediamine were dissolved in 566.6 g of deionized water, 2 g of a binder solution was obtained. It was made to adhere to the filter pad arrange | positioned in the balance, and it heated at 120 degreeC for 15 minutes. A brownish water-insoluble polymer was formed on the filter pad. The cured filter pad extract using 100 g of deionized water is essentially colorless and has a pH of 6.8.

(Example 3)
A solution (15% solid solution, pH 10.8) prepared by dissolving 85 g (0.472 mol) of dextrose and 15 g (0.129 mol) of hexamethylenediamine in 566.6 g of deionized water was prepared. 2 g of the binder solution was attached to a filter pad placed in a moisture balance and heated at 140 ° C. for 15 minutes. A brownish water-insoluble polymer was formed on the filter pad. The cured filter pad extract using 100 g of deionized water is essentially colorless and has a pH of 6.8.

Example 4
A solution (15% solid solution) in which 95 g (0.528 mol) of dextrose and 5 g (0.043 mol) of hexamethylenediamine were dissolved in 566.6 g of deionized water was prepared. 2 g of the binder solution was attached to the filter pad placed in the moisture balance and heated at 180 ° C. for 15 minutes. A brownish water-insoluble polymer was formed on the filter pad. The cured filter pad extract using 100 g of deionized water is essentially colorless and has a pH of 6.8.

(Comparative Example 1)
A solution (15% solid content solution) in which 180 g (1 mol) of dextrose was dissolved in 1020 g of deionized water was prepared. 2 g of the binder solution was attached to the filter pad placed in the moisture balance and heated at 180 ° C. for 15 minutes. No water insoluble polymer was formed on the filter pad. The resulting heat treated binder was essentially completely water soluble.

Curing speed and curing time: A square glass fiber mat (13 ″ × 13 ″) weighing 44 g (corresponding to 34.5 g / ft ² ) was impregnated with a binder containing 15% solids. Excess binder is removed by vacuum suction and the wet mat is dried in an oven (recirculation) at 90 ° F. for at least 12 hours.

Cut the dried mat into 4 squares of the same dimensions. Squares stacked on top of each other and at least one thermocouple connected to the recorder (ie, oven mole)
) In the center of the stack between the second and third layers.

  A forming press equipped with a temperature controlled platen is heated to 400 ° F. (204 ° C.). A sample with the prepared thermocouple is placed in the center of the platen and is 5/8 "thick for a predetermined time (ie 3.5 minutes, 4.0 minutes, 5.0 minutes, 6.0 minutes, 15 minutes) Press.

  Each molded sample was evaluated for degree of cure by testing surface uniformity, water hold-up properties, and extracts. The sample has a smooth surface with no “kumps”, the sample does not weaken significantly when the sample is immersed in water, and no significant coloration of the extract is formed when the sample is immersed in water The sample was considered cured. The temperature profile at the center of the sample was measured during the molding cycle and is shown in FIG.

(Comparative Example 2)
Phenol formaldehyde binder.
Composition based on dry solids:
-Ammonium sulfate 2.41 parts-Ammonia 1.08 parts-Silane A1101 0.21 parts-96.3% phenol formaldehyde resin: Urea Premix (70:30)
Comparative Example 2 is referred to as Binder 1 in FIG.

(Comparative Example 3)
Carbohydrate-inorganic acid binder.
Composition based on dry solids:
-Dextrose 81.59 parts-Ammonium sulfate 17.09 parts-Ammonia 1 part-Silane A1101 0.3 part The comparative example 3 is called the binder 2 in FIG.

(Example 5)
Composition based on dry solids:
-Dextrose and ammonia solution (aqueous solution containing 2 mol / l dextrose and 2 mol / l ammonia) 80.94 parts-hexamethylenediamine 19.06 parts Example 5 is referred to as binder 4 in FIG.

  It was determined that the time required to achieve full cure of the binder within the scope of the present disclosure was shorter than for the three comparative binder systems with various chemistries. This model system shows that the cure time depends on the chemistry of the binder system, assuming that other variables remain constant. The chemistry of exemplary binder compositions within the scope of this disclosure provides improved cure times compared to these other exemplary systems. The results are shown below.

次に図３を参照すると、結合剤１、２、および４のそれぞれに特徴的な温度プロファイルが示されている。温度プロファイルは各結合剤ごとに特徴的であることがわかった。硬化速度および硬化時間が硬化温度プロファイルの特徴でないことは、立証されなかった。しかし硬化温度プロファイルは、硬化速度および硬化時間を理解し予測するのを助ける。具体的には、比較例３は最長の硬化時間を必要とし、同様に硬化温度プロファイルは、漸近的に最大限にするのに最も長い時間を必要とした。同様に、実施例５は、漸近的に最大限にするのに最も短い時間を必要とし、最短の硬化時間を実証した。

Referring now to FIG. 3, characteristic temperature profiles for each of the binders 1, 2, and 4 are shown. The temperature profile was found to be characteristic for each binder. It was not established that the cure rate and cure time were not characteristic of a cure temperature profile. However, the cure temperature profile helps to understand and predict cure speed and cure time. Specifically, Comparative Example 3 required the longest cure time, and similarly the cure temperature profile required the longest time to asymptotically maximize. Similarly, Example 5 required the shortest time to asymptotically maximize and demonstrated the shortest cure time.

  Effect of carbohydrate reactant: polyamine ratio on cure cycle time. Wet raid mats (WLM) were made using dextrose monohydrate (DMH) and hexamethylenediamine (HMDA) in various ratios. The weight ratios tested included 75/25, 85/15, and 92/8, respectively.

  A 15% dextrose-HMDA binder was attached to the five WLMs. The following binder composition was prepared.

マットを、厚さ３／８”の１３”×１３”の小片に調製する。マットの成型に使用したプレスを４００°Ｆに設定する。サンプルが成型されると、その厚さは約５／８”である。温度プロファイルを、１５分間隔で最初に決定した。次のサンプルを４分間プレスした。これは、同等のフェノールホルムアルデヒド結合剤組成物を硬化するのに要する時間である（結果は図示せず）。各組成物を硬化するのに必要な最短時間が決定されるまで、実験を、様々な硬化時間で繰り返した。各結合剤が硬化するまでの範囲を、重量に基づいて決定した。下記の結果が決定された。

The mat is prepared into 13 "x 13" pieces of 3/8 "thickness. The press used to mold the mat is set to 400 ° F. Once the sample is molded, its thickness is about 5 / 8 ". The temperature profile was first determined at 15 minute intervals. The next sample was pressed for 4 minutes. This is the time required to cure an equivalent phenol formaldehyde binder composition (results not shown). The experiment was repeated at various cure times until the minimum time required to cure each composition was determined. The range until each binder was cured was determined based on weight. The following results were determined:

上述のように、同等のフェノールホルムアルデヒドをベースにした生成物（例えば、比較例２）は、４分のサイクル時間で硬化する。さらに、同等の炭水化物をベースにした結合剤（例えば、比較例３）は、５分のサイクル時間で硬化する。これらの結果は、炭水化物反応物と第一級ポリアミンとが８５／１５以下である本開示の範囲内にある結合剤が、フェノールホルムアルデヒドをベースにした生成物と同等のまたはそれよりも速い速度で硬化することを示す。さらなる実験は、より低い温度で等しい硬化時間を実現するために、より短い硬化時間を有する生成物において硬化温度を下げることができることを示した。得られた結果は、アレニウスの式に基づいた本発明者らの予測に基本的には一致した。

As mentioned above, an equivalent phenol formaldehyde-based product (eg, Comparative Example 2) cures in a 4 minute cycle time. Furthermore, an equivalent carbohydrate based binder (eg, Comparative Example 3) cures in a cycle time of 5 minutes. These results show that binders within the scope of this disclosure in which the carbohydrate reactant and primary polyamine are 85/15 or less are at a rate comparable to or faster than products based on phenol formaldehyde. Indicates to cure. Further experiments have shown that the curing temperature can be lowered in products with shorter curing times in order to achieve equal curing times at lower temperatures. The obtained results basically agreed with the inventors' prediction based on the Arrhenius equation.

  In addition to those examples detailed, the following examples were performed to ensure that the carbohydrate reactants and polyamines may include a wide range of alternatives.

他のデキストロース−求核剤の実施例：
（実施例１６）
脱イオン水５６．０８ｇ、デキストロース一水和物７．１５ｇ、および１，１２−ジアミノドデカン３．５ｇの懸濁液を、１１Ｎ ＨＣｌでｐＨ１．０に酸性化し、撹拌しながら７０℃に加熱した結果、無色透明の溶液が得られた。溶液は、熱硬化性の水不溶性ポリマーを１６０℃で形成する（試験条件：結合剤溶液２ｇを、モイスチャーバランス内に配置したフィルターパッドに付着させる。フィルターパッドを１６０℃で１５分間加熱する）。脱イオン水１００ｇによる硬化したフィルターパッドの抽出物は、本質的に無色である。

Examples of other dextrose-nucleophiles:
(Example 16)
A suspension of 56.08 g deionized water, 7.15 g dextrose monohydrate, and 3.5 g 1,12-diaminododecane was acidified to pH 1.0 with 11 N HCl and heated to 70 ° C. with stirring. As a result, a colorless and transparent solution was obtained. The solution forms a thermosetting water-insoluble polymer at 160 ° C. (Test conditions: 2 g of binder solution is deposited on a filter pad placed in the moisture balance. The filter pad is heated at 160 ° C. for 15 minutes). The cured filter pad extract with 100 g of deionized water is essentially colorless.

(Example 17)
A solution prepared by dissolving 8.25 g of dextrose monohydrate and 2.50 g of 1,5-diamino-2-methylpentane (Dytek A, Invista) in 56.08 g of deionized water is obtained by adding a thermosetting water-insoluble polymer. Form at 160 ° C. (Test conditions: 2 g of binder solution are attached to the filter pad placed in the moisture balance. Heat the filter pad at 160 ° C. for 15 minutes). The cured filter pad extract with 100 g of deionized water is essentially colorless.

(Example 18)
A solution obtained by dissolving 8.03 g of dextrose monohydrate and 2.70 g of N- (3-aminopropyl) -1,3-propanediamine in 56.08 g of deionized water is obtained by adding a thermosetting water-insoluble polymer to 200. (Test condition: 2 g of binder solution is deposited on the filter pad placed in the moisture balance. Heat the filter pad at 200 ° C. for 15 minutes). The cured filter pad extract with 100 g of deionized water has a slightly yellowish color.

(Example 19)
A solution prepared by dissolving 3 g (0.016 mol) of dextrose and 0.5 g (0.004 mol) of hexamethylenediamine in 9 mL of deionized water was prepared. The reaction mixture was heated at 100 ° C. for 1 hour, after which 0.7 g (0.004 mol) dithiothreitol was added to the mixture, which was added dropwise to the filter pad, and the filter pad was heated at 125 ° C. A brownish water-insoluble polymer was formed on the filter pad.

(Example 20)
A solution was prepared by dissolving 3 g (0.016 mol) of dextrose and 0.5 g (0.004 mol) of hexamethylenediamine in 9 mL of deionized water. The reaction mixture was heated at 100 ° C. for 1 hour, after which 0.52 g (0.004 mol) butanedithiol was added to the mixture, which was added dropwise to the filter pad, and the filter pad was heated at 125 ° C. A brownish water-insoluble polymer was formed on the filter pad.

  Procedure for analyzing binder samples by gas pyrolysis. About 10 g of cured product with binder on the surface is placed in a test tube, then the test tube is heated to 1000 ° F. for 2.5 minutes, at which time the headspace is sampled and gas chromatography / mass spectrometry (GC / MS) under the following conditions: furnace, 1 minute at 50 ° C. to 300 ° C. for 10 minutes; inlet, 280 ° C. splitless; column, HP-5 30 mm × 0.32 mm × 0 Column flow, 1.11 mL / min Helium; Detector, MSD 280 ° C .; Injection volume, 1 mL; Detector mode, scan 34-700 amu; Threshold, 50; and Sampling rate, 22 scans / second. A computer search of the mass spectrum of the chromatographic peak in the sample is performed against the Wiley library of mass spectra. The best match is reported. A quality index (closeness of match to the library spectrum) ranging from 0 to 99 is generated. Only those peaks that have a quality index greater than 90 are reported.

  The table below shows representative pyrolysis data as predicted from GC / MS analysis of gaseous compounds produced during the pyrolysis of binder compositions based on melanoidins.

下記は、ポリアミン構成成分としてヘキサメチレンジアミンを使用して調製された結合剤サンプルの熱分解ガスクロマトグラフィー質量分析法（ＰｙＧＣ−ＭＳ）で観察された、化学種を挙げたものである。熱分解は、２００℃、３００℃、および７７０℃で実施した。フィンガープリントは、２００℃および３００℃の両方で、質量クロマトグラムにおいて酢酸に相当する非常に有意なピークを示し、これは、デキストロースおよび硫酸アンモニウムを使用して作製されたサンプル（比較例３参照）では見られないものであり、有意な揮発物質は特に３００℃でのＳＯ_２であった。７７０℃で、観察されたピークを、保持時間が増加する順に、下記の通り割り当てた：Ａ：共溶出されるＣ_５Ｈ_１０、Ｃ_５Ｈ_１２、アセトン、おそらくは低分子量の酢酸エステル；Ｂ：Ｃ_５Ｈ_８ジエン；Ｃ：Ｃ_５Ｈ_８ジエン；Ｄ：おそらくはペンタノール；Ｅ：Ｃ_６Ｈ_１２−メチルペンテン；Ｆ：ヘキサン；Ｇ：メチルシクロペンタン；Ｈ：シクロヘキサジエン；Ｉ：Ｃ_６Ｈ_１０−おそらくはメチルシクロペンタン；Ｊ：ベンゼン；Ｋ：酢酸；Ｌ：シクロヘキセン；Ｍ：おそらくはノナノール；Ｎ：２−メチル−３−ペンタノン；Ｏ：２，５−ジメチルフラン；Ｐ：Ｃ_７Ｈ_１０＋未割当共溶出物；Ｑ：ピリジン＋未割当共溶出物；Ｒ：トルエン；Ｓ：おそらくはデセナール＋未割当共溶出物；Ｔ：２−エチル−５−メチルフラン；Ｕ：メチルピリジン；Ｖ：メチルピロール；Ｗ：キシレン；Ｘ：未割当（これはアルコール官能性を有する）；Ｙ：未割当；Ｚ：キシレン＋未割当共溶出物；ＡＡ：未割当；ＡＢ：ジメチルピロール；ＡＣ：ジメチルピリジン；ＡＤ：ジメチルピリジン；ＡＥ：未割当；ＡＦ：未割当；ＡＧ：エチルメチルピロール＋未割当共溶出物；ＡＩ：未割当であるが明瞭な質量スペクトル（Ｎ含有）、ピロール関連；ＡＪ：未割当であるが明瞭な質量スペクトル（Ｎ含有）、おそらくはアセトアミド；ＡＫ：未割当であるが明瞭な質量スペクトル（Ｎ含有）、ピロール関連；ＡＬ：未割当であるが明瞭な質量スペクトル（Ｎ含有）ピロール関連；ＡＭ：未割当であるが明瞭な質量スペクトル（Ｎ含有）、ピロール関連。ピークＡＩからＡＭに見られる明瞭な質量スペクトルは、ポリアミン構成成分を持たない従来の結合剤のデータでは見られない。

The following lists the chemical species observed by pyrolysis gas chromatography mass spectrometry (PyGC-MS) of binder samples prepared using hexamethylenediamine as a polyamine component. Pyrolysis was performed at 200 ° C, 300 ° C, and 770 ° C. The fingerprint shows a very significant peak corresponding to acetic acid in the mass chromatogram at both 200 ° C. and 300 ° C., which is the case for samples made using dextrose and ammonium sulfate (see Comparative Example 3). Not seen and significant volatiles were SO ₂ at 300 ° C. in particular. At 770 ° C., the observed peaks were assigned in the order of increasing retention time as follows: A: co-eluted C ₅ H ₁₀ , C ₅ H ₁₂ , acetone, possibly low molecular weight acetate; B: C: C ₅ H ₈ diene; C: C ₅ H ₈ diene; D: probably pentanol; E: C ₆ H ₁₂ -methylpentene; F: hexane; G: methylcyclopentane; H: cyclohexadiene; I: C ₆ H ₁₀ - perhaps methylcyclopentane; J: benzene; K: acetic acid; L: cyclohexene; M: perhaps nonanol; N: 2-methyl-3-pentanone; O: 2,5-dimethyl _{furan; P:} C _{7 H 10} + Unassigned co-eluted; Q: pyridine + unassigned co-eluted; R: toluene; S: possibly decenal + unassigned co-eluted; T: 2-ethyl-5-methyl U: methyl pyridine; V: methyl pyrrole; W: xylene; X: unassigned (which has alcohol functionality); Y: unassigned; Z: xylene + unassigned co-eluate; AA: unassigned; AB: dimethylpyrrole; AC: dimethylpyridine; AD: dimethylpyridine; AE: unassigned; AF: unassigned; AG: ethylmethylpyrrole + unassigned co-eluate; AI: unassigned but clear mass spectrum (N Containing), pyrrole related; AJ: unassigned but clear mass spectrum (N containing), possibly acetamide; AK: unassigned but clear mass spectrum (N containing), pyrrole related; AL: unassigned Is clear mass spectrum (N-containing) pyrrole-related; AM: unallocated but clear mass spectrum (N-containing), pyrrole-related. The clear mass spectrum seen from peaks AI to AM is not seen in the data for conventional binders that do not have a polyamine component.

  Procedure for assessing drying and weathering tensile strength. When evaluated for their dry and "weather" tensile strength, glass bead-containing shellbone compositions prepared with a given binder are similar to glass fiber products prepared with that particular binder. Each provides an indication of tensile strength and similar durability. The predicted durability is based on the ratio of weathering tensile strength: dry tensile strength of the shellbone. Shellbone is prepared, exposed to the weather, and tested as follows, for example, for a hexamethylenediamine-dextrose binder mixture.

  Set the shell bone mold (Diet Foundry Testing Equipment; Heated Shell Curing Accessory, Model 366, and Shell Mold Accessory) to the desired temperature, typically 425 ° F., and heat up for at least 1 hour. While heating the shellbone mold, about 100 g of an aqueous binder (generally 15% binder solids) is prepared (eg, as described in Example 7). Using a large glass beaker, weigh out 727.5 g of glass beads (Quality Ballotini Impact Beads, Spec. AD, US Sieve 70-140, 106-212 micron- # 7, Potters Industries, Inc.). The glass beads were poured into a clean and dry mixing bowl and the bowl was placed on an electric mixer stand. Slowly pour about 75 g of aqueous binder onto the glass beads in the mixing bowl. The electric mixer is then turned on and the glass bead / binder mixture is stirred for 1 minute. Using a large spatula, scraping the sides of the whisker (mixer) removes all of the binder mass, as well as the edges where the glass beads are present on the bottom of the bowl. The mixer is then turned on for an additional minute, then the whisk (mixer) is removed from the unit, and then the mixing bowl containing the glass bead / binder mixture is removed. Use a large spatula to remove as much binder and glass beads as possible attached to the whisk (mixer) and then mix into the glass bead / binder mixture in the mixing bowl. The side of the bowl is then scraped and mixed with any excess binder that may have accumulated on the side. At this point, the glass bead / hexamethylenediamine-dextrose binder mixture is ready to be molded in a shellbone mold.

  The shellbone mold slide is confirmed to be aligned within the bottom mold platen. A large spatula is then used to quickly add the glass bead / hexamethylenediamine-dextrose binder mixture to the three mold cavities in the shellbone mold. The surface of the mixture in each cavity is leveled, while excess mixture is rubbed off to give the shell bone a uniform surface area. Any mismatches and gaps present in any of the cavities are filled with additional glass bead / hexamethylenediamine-dextrose binder mixture and then leveled flat. Once the glass bead / hexamethylenediamine-dextrose binder mixture is placed in the shellbone cavity, the mixture is exposed to heat to initiate curing. The operating time can affect the test results, and the shell bone is consistently and rapidly prepared, for example, because a shell bone having a layer cured in two different states can be produced. Once the shellbone mold is filled, quickly place the top platen on the bottom platen. At the same time or shortly thereafter, the cure time measurement is initiated using a stopwatch, during which the bottom platen cure temperature ranges from about 400 ° F to about 430 ° F, while the top platen temperature is about 440 ° F. From F to about 470 ° F. At an elapsed time of 7 minutes, the upper platen is removed and the slide is pulled out so that all three shell bones can be removed. The newly created shell bone is then placed on a wire rack adjacent to the shell bone mold platen and allowed to cool to room temperature. Thereafter, each shell bone is labeled and each shell bone is placed individually in an appropriately labeled plastic storage bag. If the shellbone could not be tested on the day it was prepared, a shellbone-containing plastic bag was placed in the desiccator unit.

  Shellbone conditioning (weathering) procedure: Turn on the Blue M humidity chamber and then set it to provide weathering conditions of 90 ° F and 90% relative humidity (ie 90 ° F / 90% rH) . Check the water tank on the side of the humidity chamber and fill it regularly, usually every time you turn it on. The humidity chamber is allowed to reach specified weathering conditions over a period of at least 4 hours, typically a full day of equilibration. Shellbones that are exposed to weathering conditions are quickly put into the slotted shelf above the humidity chamber through the open humidity chamber door, one at a time (both humidity and temperature decrease while the door is open) So) Write down the time that the shellbone is placed in the humidity chamber and perform the weathering test for 24 hours. The humidity chamber door is then opened and a set of shell bones is quickly removed at once, individually placed in each plastic storage bag and completely sealed. In general, one to four sets of shell bones are simultaneously subjected to a weathering test as described above. The weather-tested shellbone is immediately brought to the Instron room for testing.

  Test procedure to destroy the shellbone: In the Instron room, the shellbone test method was introduced into the 5500R Instron machine, ensuring that the proper load cell (ie, Static Load Cell 5kN) was installed, and the machine was installed for 15 minutes. Warm up. During this period, make sure the shellbone test grip is installed on the machine. Zero the load cell, maintain balance, and then test a set of shellbones simultaneously as follows: Remove the shellbone from its plastic storage bag and then weigh. The weight (in grams) is then entered into a computer connected to the Instron machine. The measured shell bone thickness (in inches) is then entered three times as the specimen thickness into a computer connected to the Instron machine. The shellbone specimen is then placed on the grip of the Instron machine and the test is started via the keypad of the Instron machine. After removing the shellbone specimen, the measured failure point is entered into a computer connected to the Instron machine and the test is continued until a set of all shellbones has been tested.

  Effect of carbohydrate reactant: polyamine ratio on shellbone properties. Shellbones were made using dextrose monohydrate (DMH) and hexamethylenediamine (HMDA) in various ratios with silane additive (ISIO200) and tested as described above at a test rate of 25 mm / min. did. The tested weight ratios include 90/10, 85/15, 80/20, and 75/25, respectively.

（実施例）
ガラスウール（ガラス繊維）試験
２種のグルコース−ヘキサメチレンジアミン結合剤と標準結合剤との品質の比較を、ガラスウール製品（Ａｃ＋０３２ １００ｍｍ １２００ｍｍ幅；３２ｋｇ／ｍ^３−１５ｍ／分）での硬化および剛性に関して、分断強度および密度を測定することにより実施した。
結合剤１：８５％グルコース−１５％ヘキサメチレンジアミン。
結合剤２：９０％グルコース−１０％ヘキサメチレンジアミン。

(Example)
Glass Wool (Glass Fiber) Test A comparison of the quality of two glucose-hexamethylenediamine binders and a standard binder was performed on glass wool products (Ac + 032 100 mm 1200 mm width; 32 kg / m ³ -15 m / min) and With respect to rigidity, it was carried out by measuring the breaking strength and density.
Binder 1: 85% glucose-15% hexamethylenediamine.
Binder 2: 90% glucose-10% hexamethylenediamine.

  The normal breaking strength (before autoclaving) and weathering breaking strength (after autoclave) can be measured as described in International Patent Application Publication Nos. WO2008 / 089851 or WO2009 / 019235.

  Split strength for standard binders

結合剤１に関する分断強度：

Splitting strength for binder 1:

結合剤２に関する分断強度

Split strength for binder 2

試験中の観察所見：製品は、２種のグルコース−ヘキサメチレンジアミン結合剤では線上でより茶色がかっていた。

Observations during the test: The product was more brownish on the line with the two glucose-hexamethylenediamine binders.

  Conclusion: In the case of two glucose-hexamethylenediamine binders, the result of the breaking strength (which is the tensile strength in the longitudinal direction) shows a marked improvement, which is marked by three other stiffness tests (“60 °” test). -Observed in slack measured when tilted at 60 ° to the chute; "table" test-slack measured against horizontal plane; and Acermi test-slack measured at 35 cm from the edge of the table) .

(Example)
Particleboard Test A comparison of the quality of particleboard made using urea-formaldehyde binder (UF E0) and using carbohydrate polyamine (hexamethylenediamine) binder was performed under the following conditions.
Board size: 350 × 333 mm, and mainly 10 mm (2 × 20 mm).
Platen temperature: mainly 195 ° C, but also 175 and about 215 ° C.
Pressure: setting 3.5 Mpa (35 bar) -measured 35 Kg / cm ² , 56 bar for realization. Density target: 650 kg / m ³
Preform prepared before pressing.

  result

調製された全てのボードは高品質であるように見え、裂け目または脱気は観察されなかった。この炭水化物ポリアミン配合物で作製されたボードは、１５０秒間硬化させた場合に尿素ホルムアルデヒドボードに匹敵する。

All prepared boards appeared to be of high quality and no tears or degassing were observed. Boards made with this carbohydrate polyamine formulation are comparable to urea formaldehyde boards when cured for 150 seconds.

Claims (1)

  Invention described in the specification.

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